CN104854721A - Photoelectric conversion element - Google Patents

Abstract

The photoelectric conversion element has a first electrode layer, a photoelectric conversion layer, and a second electrode layer. The first electrode layer includes a first base material and a coarse film layer formed on the first base material. The photoelectric conversion layer is formed on the coarse film layer, and the second electrode layer is formed on the photoelectric conversion layer. The rough film layer is composed of a plurality of metal fine particles irregularly connected on the surface of the first base material, and the photoelectric conversion layer enters between the plurality of metal fine particles constituting the rough film layer.

Description

Photoelectric conversion element

technical field

The present invention relates to a photoelectric conversion element.

Background technique

In order to effectively utilize renewable energy, the development of technologies utilizing the photovoltaic effect is becoming more and more important. As a result of this technological development, improvements in photoelectric conversion elements have continued. The photoelectric conversion element includes a power generation type element that converts light into electrical energy, and a light emitting type element that converts electrical energy into light conversely. Both have basically the same structure, and depending on whether a photoelectric conversion material or a light-emitting material is used for a layer arranged between electrodes, the former is a power-generating element and the latter is a light-emitting element.

As the former, a typical element is a solar cell, and as the latter, a typical element is a light emitting diode. Solar cells include inorganic solar cells and organic solar cells. As inorganic solar cells, there are crystalline (polycrystalline) silicon solar cells made of silicon, amorphous silicon solar cells, and CIGS (Copper Indium Gallium DiSelenide, Copper Indium Gallium DiSelenide) solar cells using compound semiconductors. And, as the market expands, low-cost and high-performance solar cells are required. In addition, organic thin-film solar cells exist as organic solar cells. This solar cell uses dyes and polymers as raw materials, so the cost of materials is relatively low. In addition, since a printing technique such as coating can be used, the manufacturing process is easy, and significant cost reduction and area enlargement are possible.

By mixing a p-type semiconductor as a donor material and an n-type semiconductor as an acceptor material to form a bulk heterogeneous layer, the conversion efficiency of an organic thin film solar cell can be improved. Especially, it is better to increase the P-N junction interface.

Fig. 5 is a cross-sectional view of a conventional photoelectric conversion element (the type that converts light into electric energy). This photoelectric conversion element has a substrate 11 , a first electrode layer 13 formed on the substrate 11 , a photoelectric conversion layer 14 , and a second electrode layer 17 . In addition, in order to improve conversion efficiency, a method of enlarging the surface area of the first electrode layer 13 and a method of improving efficiency by utilizing the surface plasmon effect are being actively developed.

On the other hand, in order to improve the performance of the organic EL element, which is a kind of light-emitting diode, the following researches are being actively carried out: research on improving the electron injection efficiency by forming unevenness on the electrode surface; The study of enhancing luminous efficiency by interacting electrodes with adjacent light emitters.

In addition, Patent Documents 1 to 3 and Non-Patent Documents 1 and 2 are known as prior art document information related to the present invention, for example.

prior art literature

patent documents

Patent Document 1: Japanese Patent Laid-Open No. 2006-245074

Patent Document 2: Japanese Patent Laid-Open No. 2005-310388

Patent Document 3: Japanese Patent Application Laid-Open No. 59-198781

non-patent literature

Non-Patent Document 1: J.Phys.Chem.C 2007, 111, 7218-7223

Non-Patent Document 2: Appl. Phys. Lett. 96, 043307 (2010)

Contents of the invention

The photoelectric conversion element of the present invention has a first electrode layer, a photoelectric conversion layer, and a second electrode layer. The first electrode layer includes a first substrate and a coarse film layer formed on the first substrate. The photoelectric conversion layer is formed on the coarse film layer, and the second electrode layer is formed on the photoelectric conversion layer. The rough film layer is composed of a plurality of metal fine particles irregularly connected on the surface of the first base material, and the photoelectric conversion layer enters between the junctions formed of the plurality of metal fine particles.

According to this structure, the electrode area of the photoelectric conversion element increases, and the mechanical strength of the electrode itself and the interface between the electrode and the substrate can be improved. In addition, by forming the metal particles into a thin rough film, the surface plasmon effect can be controlled and the characteristics can be improved.

Description of drawings

FIG. 1 is a schematic cross-sectional view of a photoelectric conversion element according to Embodiment 1 of the present invention.

2 is a schematic cross-sectional view of another photoelectric conversion element according to Embodiment 1 of the present invention.

3 is a schematic cross-sectional view of a photoelectric conversion element according to Embodiment 2 of the present invention.

4 is a schematic cross-sectional view of a photoelectric conversion element according to Embodiment 3 of the present invention.

Fig. 5 is a schematic cross-sectional view of a conventional photoelectric conversion element.

Detailed ways

Before describing the embodiments of the present invention, problems in conventional photoelectric conversion elements will be described. When forming the conventional photoelectric conversion element shown in FIG. 5 , the photoelectric conversion layer 14 and the first electrode layer 13 as a counter electrode are formed sequentially from the second electrode layer 17 as a transparent electrode layer.

According to Non-Patent Document 1, in order to improve the conversion efficiency, it is desirable to increase the surface area (enlargement of the area) per area of the first electrode layer 13 for incident and light emission. The first electrode layer 13 is formed on the base material 11 , so it is generally necessary to perform high temperature treatment on the base material 11 such as oxides. For this reason, the type of base material 11 is limited. Therefore, there is a problem in forming the first electrode layer 13 by enlarging the area using a flexible substrate as the base material 11 .

Patent Document 3 describes that fine unevenness is formed on the surface of the electrode layer in contact with the photoelectric conversion layer by vapor deposition. However, this vapor deposition is a complicated process and has various limitations. In addition, as shown in Patent Document 3, it is difficult to further enlarge the area in the structure in which the unevenness is formed in an island shape.

In Non-Patent Document 1 and Non-Patent Document 2, an oxide is formed as the first electrode layer 13 . In this case, the mechanical strength of the electrode layer itself and the mechanical strength of the interface between the electrode layer and the substrate are small.

As described above, it is difficult to obtain sufficient mechanical strength while enlarging the area of the first electrode layer in conventional photoelectric conversion elements. In particular, these problems are conspicuous in the case of forming a photoelectric conversion element on a flexible substrate.

Next, with reference to the drawings, a photoelectric conversion element according to an embodiment of the present invention will be described. The photoelectric conversion element enlarges the area of the electrode, reduces surface plasmon absorption or surface plasmon loss, and improves the mechanical strength of the electrode itself, and the electrode and the surface plasmon. The mechanical strength of the interface of the substrate. In addition, components having the same configuration as those in the previously described embodiment are described with the same reference numerals, and detailed description may be omitted.

(Embodiment 1)

FIG. 1 is a schematic cross-sectional view of a photoelectric conversion element 31 according to Embodiment 1 of the present invention. A photoelectric conversion element (hereinafter referred to as an element) 31 has a conductive first electrode layer 3 , a photoelectric conversion layer (hereinafter referred to as a conversion layer) 4 , and a second electrode layer 7 . The first electrode layer 3 includes a conductive first substrate 1 and a coarse film layer 2 formed on the first substrate 1 . The conversion layer 4 is formed on the coarse film layer 2 so as to cover the entire surface of the first substrate 1 . A second electrode layer 7 is formed on the conversion layer 4 . Element 31 is capable of converting light into electrical energy.

The rough film layer 2 is composed of a plurality of irregularly connected metal particles 2 a connected to the surface of the first substrate 1 . In addition, when the first electrode layer 3 is taken out alone, the rough film layer 2 has many pores inside. Therefore, the conversion layer 4 enters between the connected bodies 2b formed of the plurality of metal fine particles 2a. The second electrode layer 7 is composed of a conductive layer 5 formed on the conversion layer 4 and a second base material 6 formed on the conductive layer 5 .

In the element 31 , when light enters the second electrode layer 7 , holes (holes) and electrons are generated in the conversion layer 4 . Holes move in the film thickness direction of conversion layer 4 and are extracted from conductive layer 5 , and electrons are extracted from first electrode layer 3 .

Each structure of such an element 31 will be described below. First, the first electrode layer 3 will be described. As described above, the first electrode layer 3 assumes the role of an electrode (electron extraction electrode) for extracting electrons generated by the conversion layer 4 . Since light enters the second electrode layer 7, the first electrode layer 3 does not have to be transparent.

Coarse film layer 2 is composed of a plurality of connected bodies 2 b formed such that a plurality of metal microparticles 2 a are irregularly connected and protrude from the surface of first base material 1 . The connection body 2b is a structure branched into a plurality of branches and does not have an acute-angled portion. Therefore, as described above, when the first electrode layer 3 is taken out alone, the coarse film layer 2 has many voids inside. These pores communicate with the outside, so the surface area is increased by these pores.

In addition, the connected body 2b may be formed by stacking metal fine particles 2a having substantially the same particle diameter, or may be formed by stacking metal fine particles 2a with different particle diameters at random. Alternatively, metal fine particles 2a with a large particle diameter may be arranged at the root portion, and metal fine particles 2a with a small particle diameter may be arranged at the tip portion. With such a structure, the adhesion between the metal fine particles 2a and the first substrate 1 can be improved while maintaining a large surface area.

For example, the first substrate 1 is a high-purity aluminum foil with a thickness of 10 to 50 μm, and the main component of the metal particles 2 a is also aluminum. In addition, the first base material 1 and the metal fine particles 2a can be formed of various metals such as aluminum alloy, gold, silver, copper, titanium, niobium, and tantalum. However, either of the first base material 1 and the metal fine particles 2a is preferably made of aluminum having a relatively low melting point. By constituting the rough film layer 2 with aluminum, productivity is excellent when producing it by, for example, a vapor deposition method.

The first substrate 1 may be a conductive polymer film, or transparent conductive glass, or the like. It may also be a substrate provided with a conductive film on an insulator. That is, the first base material 1 may be any base material as long as it has conductivity.

In addition, the main components of the rough film layer 2 and the first base material 1 may be different, but the same metal is preferably used. By selecting such a material, the first base material 1 can be moderately softened by the heat during vapor deposition, and the bond between the first base material 1 and the metal fine particles 2 a can be strengthened while maintaining the shape of the first base material 1 .

As described above, the first base material 1 preferably has electrical conductivity. However, the first base material 1 may function only as a base material supporting the coarse film layer 2 . In this case, the first base material 1 may not have conductivity. In this structure, the coarse film layer 2 assumes the conductive function of the first electrode layer.

Coarse film layer 2 can be formed through the following procedure.

(1) The first base material 1 is arranged in a vapor deposition tank, and a vacuum state of 0.01 to 0.001 Pa is maintained.

(2) In the periphery of the first base material 1 , an inert gas whose flow rate is 2 to 6 times that of oxygen is flowed into the argon gas so that the pressure around the first base material 1 is 10 to 30 Pa.

(3) The temperature of the first base material 1 is kept in the range of 150 to 300°C.

(4) The rough film layer 2 is formed by vacuum vapor deposition in a state where aluminum is disposed on the vapor deposition source.

In addition, in the above-mentioned step (2), vapor deposition may be performed without flowing oxygen gas and argon gas.

The rough film layer 2 can be formed through the above process. The thickness of the rough film layer 2 is preferably, for example, not less than 5 nm and not more than 10.0 μm. The surface area of the first electrode layer 3 can be increased by setting the thickness of the rough film layer 2 to be 5 nm or more. In addition, when the rough film layer 2 is extremely thin, the sheet resistance becomes too large. When the thickness of the rough film layer 2 is 10.0 μm or less, the light incident on the second base material 6 can easily reach the conversion layer 4 .

In addition, in the above description, an example of vapor deposition was given as a process for forming the rough film layer 2, but as long as a sparse structure in which a plurality of metal fine particles 2a are connected and gaps are formed between the respective metal fine particles 2a can be formed, , methods other than vapor deposition can also be used. For example, the rough film layer 2 may be formed by etching the surface of the first base material 1 .

The average particle diameter of the metal fine particles 2 a is preferably not less than 5 nm and not more than 300 nm, for example, about 100 nm. That is, the mode of the diameter of the metal fine particle 2a is 5 nm or more and 300 nm or less. When the average particle diameter is less than 5 nm, the connecting portion of the metal microparticles 2a may be extremely thin, and the mechanical strength may be weakened. In addition, when the average particle diameter exceeds 300 nm, it becomes difficult to increase the surface area. In addition, in order to maintain mechanical strength, the diameter of the connection portion of the metal fine particles 2a is preferably 30% or more of the particle diameter of the metal fine particles 2a.

In addition, in the state of the first substrate 1 alone, the mode of the pore diameter of the coarse film layer 2 is preferably 5 nm or more and 1 μm or less. In this way, the pore diameter of the coarse film layer 2 is preferably extremely small. The pore diameter of the coarse film layer 2 can be obtained from the formula (1) using the mercury intrusion porosimetry.

D＝-4γcosθ/P (1)

P is the pressure applied to fill the pores with mercury, D is the pore diameter (diameter), γ is the surface tension of mercury (480 dyne·cm ^-1 ), and θ is the contact angle between mercury and the pore wall. The mode of the pore diameter is the peak value of the distribution of the pore diameter D.

In addition, in the state of the first base material 1 alone, the porosity of the rough film layer 2 is about 50% to 80%. The porosity can be obtained by calculation based on the weight and volume of the rough film layer 2 and the true density of the vapor deposition material.

In addition, as shown in FIG. 1 , the rough film layer 2 is composed of a connected body 2 b in a state where a plurality of metal fine particles 2 a are bonded. Therefore, in the cross section in the vertical direction (stacking direction), there are many connecting portions between the particles of the metal fine particles 2a, and it may be difficult to measure the diameter of each particle. In this case, the measurement of the average particle diameter of the metal microparticles 2 a is facilitated by image processing a scanning electron microscope (SEM) photograph of a horizontal cross section of the particles.

As described above, in the coarse film layer 2, a plurality of metal fine particles 2a such as aluminum are connected and formed from the first base material 1 toward the surface layer. Therefore, it is possible to increase the electrode area, increase the contact interface with the conversion layer 4 formed on the surface, and improve interface reliability. In addition, it is preferable that the connection body 2b is formed by branching into a plurality of branches. As a result, the electrode area is further increased, and the contact interface with the conversion layer 4 is increased.

Next, conversion layer 4 will be described. As shown in FIG. 1 , the conversion layer 4 is formed to cover the entire rough film layer 2 formed on the first base material 1 . The conversion layer 4 contributes to charge separation of the element 31 and has a function of transporting generated electrons and holes to the first electrode layer 3 and the second electrode layer 7 in opposite directions, respectively.

The conversion layer 4 is shown as a single layer having both electron-accepting and electron-donating functions, but an electron-accepting layer having an electron-accepting function and an electron-donating layer having an electron-donating function may be laminated. And formed. An example composed of a single layer will be described below.

The conversion layer 4 contains an electron donating material and an electron accepting material. Therefore, charge separation is generated by the P-N junction formed in the conversion layer 4, so that photoelectric conversion can be performed independently. The electron donating material is not particularly limited as long as it has the function of an electron donor. In addition, the electron-accepting material is not particularly limited as long as it has a function as an electron acceptor. However, these materials are preferably conductive polymer materials. If it is a conductive polymer material, film formation by a wet coating method is also possible, and a large-area photoelectric conversion element can be manufactured at low cost.

In particular, poly-3-hexylthiophene (P3HT) is preferably used as a p-type organic semiconductor, and fullerenes such as [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) are preferably used as an n-type organic semiconductor. derivative. By mixing these materials, a so-called bulk heterogeneous photoelectric conversion layer can be formed.

The film thickness of the conversion layer 4 is preferably within a range generally employed in bulk heterogeneous photoelectric conversion elements. Specifically, in order to cover the entire coarse film layer 2 , it is preferably thicker than the thickness of the coarse film layer 2 . Therefore, it is preferably in the range of 5 nm or more and 10.0 μm or less.

The mixing ratio of the electron-donating material and the electron-accepting material is appropriately adjusted to an optimal mixing ratio according to the type of materials used.

The method of forming conversion layer 4 is not particularly limited as long as it can be uniformly formed to a predetermined film thickness. Among such methods, a wet coating method is preferably used. According to the wet coating method, the conversion layer 4 can be formed in the air, and it is possible to reduce the cost and increase the area. That is, the conversion layer 4 can be formed by a manufacturing method such as die coating, spin coating, dip coating, roll coating, spray coating, gravure coating, inkjet, and screen printing, for example.

Next, the second electrode layer 7 will be described. The conductive layer 5 constituting the second electrode layer 7 is formed on the conversion layer 4 and is made of a conductive material. In particular, it is preferable to use a translucent conductive material made of a metal oxide such as ITO. Such conductive layer 5 can be formed by various methods such as a coating method, a sputtering method, and an electrolytic polymerization method. Alternatively, the conductive layer 5 capable of transmitting light may be formed using a mesh structure using metal particles or the like.

On the other hand, since the second base material 6 serves as a light-receiving surface, it is preferably formed of a transparent material. The transparent material is not particularly limited, and for example, non-flexible transparent rigid materials such as quartz glass and synthetic quartz plates, or flexible transparent flexible materials such as transparent resin films and optical resin plates can be used. In addition, it is not necessary to cover the entire surface of the element 31 with the second electrode layer 7, and it may be in a grid shape. In this case, the second electrode layer 7 does not necessarily have to be formed of a transparent material. That is, the second electrode layer 7 can be constituted by metal mesh wiring electrodes and metal nanowire electrodes.

In addition, in the above, the second base material 6 is preferably a flexible material such as a transparent resin film. The transparent resin film is light, has excellent processability, and can reduce manufacturing costs. In addition, since it is formed of an organic material, it has high reliability against external stress such as bending. Therefore, by improving the flexibility, it is possible to apply the element 31 to a non-flat curved surface shape as an application of the element 31 .

In the conventional photoelectric conversion element shown in FIG. 5 , the adhesion between the first electrode layer 13 and the photoelectric conversion layer 14 is low, and the interface between the first electrode layer 13 and the photoelectric conversion layer 14 cannot obtain sufficient reliability. In particular, when the first electrode layer 13 is made of an inorganic material and the photoelectric conversion layer 14 is made of an organic material, the adhesion between the two is low, and sufficient interface reliability cannot be obtained. In addition, if the photoelectric conversion element is required to have flexibility, long-term interface reliability is important.

After the second electrode layer 7 is formed, a post-processing step can be performed by applying pressure from at least one of the upper and lower surfaces of the element 31 . Alternatively, as shown in FIG. 2 , a laminate having the same structure as the element 31 may be packaged in an insulating exterior member 20 in a decompressed state to form a photoelectric conversion element (hereinafter referred to as element) 32 . By forming each layer as a unit and finally applying pressure or sealing with the outer package member 20 which is a vacuum package, the bonding of each layer can be performed, and the function as an electronic device can be improved. In addition, the vacuum degree of the vacuum packaging is preferably 100 Pa or less. As a result, the adhesion between the first electrode layer 3 and the conversion layer 4 can be improved, and the bonding reliability at the interface between the first electrode layer 3 and the conversion layer 4 can be improved. Preferably, the rough film layer 2 and the conversion layer 4 are crimped as described above. When the metal first substrate 1 whose surface is etched is used as the first electrode, the effect of pressing and sealing it in the insulating exterior member 20 in a depressurized state is also effective.

As described above, in the elements 31 and 32 , the area of the first electrode layer 3 can be increased compared to the case where the etching process is performed as in the related art. In addition, the contact interface between the coarse film layer 2 made of metal fine particles 2 a and the conversion layer 4 can be greatly increased. In addition, the rough film layer 2 has a special structure composed of a junction body 2b in which metal particles 2a are irregularly connected, so in addition to increasing the electrode area, it also improves photoelectric conversion efficiency through the surface plasmon absorption effect. In addition, by increasing the contact interface between the first electrode layer 3 and the conversion layer 4 , the mechanical strength of the first electrode layer 3 itself and the interface between the two increases, and the adhesion between the two increases. In addition, the traceability to bending is also improved. Therefore, the elements 31, 32 can have high reliability over a long period of time.

(Embodiment 2)

FIG. 3 is a schematic cross-sectional view of a photoelectric conversion element (hereinafter referred to as an element) 33 according to Embodiment 2 of the present invention. Compared to the structure of Embodiment 1 shown in FIG. 1 , element 33 has hole transport layer (hereinafter referred to as transport layer) 8 at the interface between conversion layer 4 and conductive layer 5 . That is, element 33 has transport layer 8 between conversion layer 4 and conductive layer 5 . Other configurations are the same as those of Embodiment 1.

By providing the transport layer 8 , the transport layer 8 in contact with the conversion layer 4 smoothes the charge transfer from the conversion layer 4 to the conductive layer 5 . Therefore, the charge (hole) extraction efficiency can be improved. As a result, photoelectric conversion efficiency can be improved.

In addition, in FIG. 3 , the transport layer 8 is formed on the entire surface of the conversion layer 4 , but may be formed on at least a part of the conversion layer 4 . The transport layer 8 is provided in direct contact with both the conversion layer 4 and the conductive layer 5 .

In the element 33 , since light enters the conversion layer 4 via the second electrode layer 7 and the transport layer 8 , the transport layer 8 has light transmittance. Specifically, the total light transmittance of the transport layer 8 is preferably 80% or more. Similarly, for the second electrode layer 7 , the total light transmittance can be made 80% or more by using a transparent electrode or a grid-shaped electrode as the conductive layer 5 .

The transport layer 8 is formed of a material capable of transporting holes. That is, the material used for the transport layer 8 is not particularly limited as long as it satisfies the above characteristics and can efficiently extract holes from the conversion layer 4 to the conductive layer 5 . Specifically, polyvinyldioxythiophene/polystyrenesulfonic acid (PEDOT/PSS) is preferred. In addition, conductive polymer materials such as doped polyaniline, polyphenylene vinylene, polythiophene, and polypyrrole can also be used.

The film thickness of the transport layer 8 is preferably within a range of not less than 5 nm and not more than 600 nm. When too thick, the volume resistivity of a film may become large.

The transport layer 8 can be formed by a wet coating method or the like. The coating method is not particularly limited as long as it can uniformly form a predetermined film thickness, and examples thereof include die coating, spin coating, dip coating, roll coating, bead coating, and spray coating. , gravure coating method, inkjet method, screen printing method, etc. After forming the transport layer 8 on at least a part of the upper surface of the conversion layer 4 by this method, the conductive layer 5 is formed in the same manner as in Embodiment 1, and the second base material 6 is placed thereon, whereby the element 33 can be produced.

(Embodiment 3)

FIG. 4 is a schematic cross-sectional view of a photoelectric conversion element (hereinafter referred to as an element) 34 according to Embodiment 3 of the present invention. In the structure of the first embodiment shown in FIG. 1 , the element 34 has a photoelectric conversion layer (hereinafter referred to as a conversion layer) 24 instead of the conversion layer 4 . If an electric field is applied between the first electrode layer 3 and the second electrode layer 7, the charges (holes) moving from the second electrode layer 7 into the conversion layer 24 and the electrons injected from the conductive layer 5 into the conversion layer 24 Combine glow. In this way, element 34 is capable of converting electrical energy into light. Other configurations are the same as those of Embodiment 1.

In this structure, the first electrode layer 3 takes on the role of an electrode (electron injection electrode) for injecting electrons into the conversion layer 24 . In the element 34 light penetrates from the conversion layer 24 to the second electrode layer 7 . Therefore, like Embodiment 1, the first electrode layer 3 does not necessarily have to be transparent.

In the element 34 , preferred ranges of the average particle diameter of the metal fine particles 2 a , the mode of the pore diameter of the coarse film layer 2 , the porosity of the coarse film layer 2 , and the thickness of the coarse film layer 2 are the same as those in the first embodiment.

Next, the conversion layer 24 will be described. As shown in FIG. 4 , the conversion layer 24 is formed to cover the entire coarse film layer 2 formed on the first base material 1 . The conversion layer 24 contributes to the light emission of the element 34, and has a function of injecting electrons and holes from the first electrode layer 3 and the second electrode layer 7 respectively, and combining the generated charges.

In FIG. 4 , the conversion layer 24 is shown as a single layer having both electron-accepting and electron-donating functions. However, an electron-accepting layer having an electron-accepting function and an electron-donating layer having an electron-donating function may be laminated. An example composed of a single layer will be described below.

The conversion layer 24 as a light emitting layer contains an electron donating material and an electron accepting material. Therefore, light is emitted by the charges recombined in the conversion layer 24 , so the light-emitting layer 24 alone functions as a light-emitting layer.

Specifically, polyparaphenylene is preferably used as the luminescent material. In addition, electron conductive polymers such as polyparaphenylene and poly(9,9 dialkylfluorene) can be used for the conversion layer 24 .

The thickness of the conversion layer 24 is preferably a film thickness generally used in polymer organic EL light-emitting devices. In addition, in order to cover the entire coarse film layer 2 , it is preferably thicker than the thickness of the coarse film layer 2 . Therefore, it is preferably in the range of 5 nm or more and 10.0 μm or less.

In addition, as described with reference to FIG. 2 in Embodiment Mode 1, after forming the second electrode layer 7, it is preferable to apply pressure from at least one of the upper and lower surfaces of the element 34, or to reduce the pressure of the laminate having the same structure as the element 34. The pressure state is encapsulated in the insulating outer packaging part. According to any of these methods, the bonding of the respective layers can be performed, and the function as an electronic device can be improved. As a result, it is possible to manufacture the element 34 with higher luminance than in the prior art.

In the above manner, in the element 34 , an increase in the electrode area can be realized as compared with the prior art, and a contact interface between the coarse film layer 2 composed of metal fine particles 2 a and the conversion layer 24 can be greatly increased. As a result, the mechanical strength of the first electrode layer 3 itself, the first electrode layer 3 and the conversion layer 24 is improved, and the adhesion between them is improved. In addition, the traceability to bending becomes better. Therefore, the element 34 can have high reliability over a long period of time. In addition, by controlling the area of the first electrode layer 3 and the film thickness of the coarse film layer 2, surface plasmon loss can be reduced, light can be extracted more efficiently, and the element 34 can also have high brightness.

In addition, for a laminate having the same structure as the element 34, as shown in FIG. The rough film layer 2 and the conversion layer 24 may also be crimped by applying pressure.

Industrial availability

The photoelectric conversion element of the present invention has the characteristics of large electrode area and high efficiency (high brightness). In addition, the photoelectric conversion element of the present invention has strong mechanical strength and high reliability, and can be applied to applications requiring flexibility, and the like.

1 first substrate

2 Coarse film layer

2a Metal particles

2b linker

3.13 The first electrode layer

4, 14, 24 photoelectric conversion layer (conversion layer)

5 conductive layer

6 Second substrate

7, 17 Second electrode layer

8 hole transport layer (transport layer)

11 Substrate

20 Outer packing parts

31, 32, 33, 34 photoelectric conversion elements (elements)

Claims (8)

1. A photoelectric conversion element, comprising: The first electrode layer has a first substrate and a coarse film layer formed on the first substrate; a photoelectric conversion layer formed on the coarse film layer; and a second electrode layer formed on the photoelectric conversion layer, The rough film layer is composed of a plurality of metal fine particles irregularly connected on the surface of the first base material, and the photoelectric conversion layer enters between a plurality of connected bodies formed of the plurality of metal fine particles. 2. The photoelectric conversion element according to claim 1, wherein The connected body has a structure branched into a plurality of branches. 3. The photoelectric conversion element according to claim 1, wherein In the state of the first base material alone, the mode of the pore diameter of the coarse film layer is not less than 5 nm and not more than 1 μm. 4. The photoelectric conversion element according to claim 1, wherein The mode of the diameter of the metal microparticles is not less than 5 nm and not more than 300 nm. 5. The photoelectric conversion element according to claim 1, wherein The second electrode layer is any one of transparent electrodes, metal mesh wiring electrodes, and metal nanowire electrodes. 6. The photoelectric conversion element according to claim 1, wherein The rough film layer and the photoelectric conversion layer are pressed together. 7. The photoelectric conversion element according to claim 6, further comprising: an insulating outer packaging member that encapsulates a laminate including the first electrode layer, the photoelectric conversion layer, and the second electrode layer in a decompressed state, The rough film layer and the photoelectric conversion layer are crimped by the outer package member. 8. The photoelectric conversion element according to claim 1, further comprising: A hole transport layer is formed between the photoelectric conversion layer and the second electrode layer.